Process for breaking petroleum emulsions employing certain oxyalkylated higher polyethylene amines



May 14, 1957 w. J. DICKSON 2,792,372

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATEDHIGHER POLYETHYLENE AMINES Filed Sept. 15, 1954 BINARY REACTION PRODUCTFOR OXYETHYLATION HIGHER POLYETHYLENE POLYAMINE cc DD PRINCIPALLY H N(CgH4NH)nCzH4 NHz BINARY WHERE n IS 4 TO 7' REACTION I003; PRODUCT FOROXYPROPYLATION INVENTOR aim Woodrow J. Dickson, Monterey Park, Califassignor to Petrolite Corporation, Wilmington, Del., a corporation ofDelaware Application September 15, 1954,- Serial No. 456,296

20 Claims. 01. 252-344 This'invention" relates to processes orprocedures particularly adapted for preventing, breaking or resolvingemulsions of the water-in-oil type, and particularly petroleumemulsions.

My invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type that are commonly referredto as cut oil, roily oil, -emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weak'brines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value inremovingimpurities particularly .inorganicsalts, from pipeline oil.

Polyethylene amines are obtained by reactions involving ammonia andethylene dichloride, followed by fractional distillation. The commonpolyamines are ethylene diamine, diethylene triamine, triethylenetetramine, and tetraethylene pentamine. Above the pentamines, i. e., thehexamines, heptamines, octamines 'and possibly nonamines, thecogenerically derived mixture does not appear to be separable bydistillation and may include also certain other materials, perhapscyclic 'amines and particularly piperazine. There may be present cyclicamines with side chains in which nitrogen atoms appear. The materials,indeed, may contain small amounts of water, for instance, 2% orthereabouts, and even a small amount of salt, forinstance, /z% or so.

The general procedure has been to sell residue from distillation simplyas higher polyethylene polyamine residue with a description as to itsmethod of production audits probable-composition, within the abovelimits. Numerous examples whichhave been examined based on anapproximate combining weight-show the product corresponds on the averageto aheptamine or thereabouts. Ignoring cyclic amines, etc., and perhapscertain unknown components present, for practical purposes the materialmaybedescribed as H2N(C2H4NH)11,C2H4NH2 where nis4 to 7.

The above formula ignores the fact there is present a small amount of alower amine, for instance, a tetraethylene pentamine, which cannot bestripped out of the residual product completely using conventionalprocesses. This is noted simply for the reason that reference issubsequently made to the number of available reactive hydrogen atomsattached to nitrogen.

-For sake of brevity reference hereafter will be made to- =nondistilledresidual polyethylene amineshaving at least 6 nitrogen atoms asconventionally produced in polyethylene polyamine manufacture.Therefore, in the specification: this. will be abbreviated further to-residualhigher polyethylene amines.

More specifically then, the present invention is concerned with aprocess for breaking petroleum emulsions employing a demulsifierincluding a cogeneric mixture of a homologous series of glycol ethers ofresidual higher polyethylene amines. The cogeneric mixture is derivedexclusively from residual higher polyethylene amines, propylene oxideand ethylene oxide in such weight proportions so the average compositionof said cogeneric mixture stated in terms of initial reactants liesapproximately within the trapezoid of the accompanying drawing in whichthe minimum residual higher polyethylene amine content is at least 1.75%and which trapezoid is identified by the fact that its area lies withinthe straight lines connecting A, .B, F, B. Our preference by far is touse the compositions which represent less thanone-half of this totalarea, to wit, the smaller trapezoid A, B, D, C.

It is immaterial as to whether one reacts the amine with propylene oxidefirst and then with ethylene oxide,-

or with ethylene oxide and then with propylene oxide; or, for thatmatter, one may employ a mixture of the two oxides; or, if desired, onemay add a small amount of ethylene oxide, then propylene oxide, and thenmore ethylene oxide.

Referring to the hereto attached drawing it is simplified by noting thatone may react residual higher polyethylene amines with enough ethyleneoxide so the binary reaction product falls within the mixture identifiedby the line CC-DD on the extremity of the graph which shows combinationsderived solely from residual higher polyethylene amines and ethyleneoxide. After obtaining such binary reaction product it can then bereacted with propylene oxide so as to bring it within the 'area of thetrapezoid A, B,'F, E, or preferably within the smaller trapezoid A, B,D, C.

Similarly, one can produce a binary reaction product from residualhigher polyethylene amines and propylene oxide as identified by thecomparable line AABB and subject this reaction product to oxyethylationso as to bring the composition within the area of the trapezoid andprefer-ably within the area of the small trapezoid A, B, D, C. For thepurpose of resolving petroleum emulsions of the Water-in-oil type, Iprefer to employ oxyalkylated derivatives, which are obtained by the useof monoepox ides,,in such manner that the derivatives so obtained have.sufficient hydrophile character to meet at least the-.tes't' set forthin U. S...Patent No. 2,499,368, dated March 7, 1950, to De Groote andKeiser. In said patent such test for emulsification using awater-insoluble solvent, generally xylene-is described as an index ofsurface activity.

The abovementioned test, i. e., a conventional emulsificationtest,simply means that the preferred product for demulsification is. solublein a solvent having hydrophobe properties or in an oxygenated waterinsoluble solvent,

or even in a mixture containing afraction of a watersoluble oxygenatedhydrocarbon solvent and that when shaken with water the product mayremain in the nonaqueous solvent or, for that matter, it may pass intothe aqueous solvent. In other words, although it is xylene soluble, for,example, it may also be water soluble to an I equal or greater degree. e

For purpose of convenience, .what is said hereinafter will be dividedinto three parts:

Part 1 is concerned with the oxyalkylation of residual higherpolyethylene amines in a general way;

Part 2 is concerned with the oxyalkylanon-of residualhigher polyethyleneamines using two different oxides, I i., e., propylene oxide andethylene'oxides so as to pro-:

Pgtented May 14, 1957.

PART 1 The oxyalkylation of amines is well known. This appliesparticularly to reactions involving monoepoxides having not over 4carbon atoms, such as ethylene oxide and propylene oxide. As to theoxyalkylation of a monoamine such as cyclohexylamine, see U; S. PatentNo. 2,626,922, dated' January 27, 1953, to De Groote. As to theoxyalkylation of a polyamine, see U. S. Patents Nos: 2,552,530,2,552,53-l and 2,552,534, all dated May 15, 1951, and all to De Groote.

Theoxyalkylation of an amine is' comparable to other well knownoxyalkylations and'under'certain conditions may require variation. Thereis no problem if the amine is a liquid or if it is xylene-soluble orsoluble in an equivalent solvent, or can be melted and reacted atthemelting point. n the case of residual higher polyethylene aminesthe'product is a liquid at ordinary temperature and all that isrequiredis to use the same procedure employed for the oxyalkylation ofa-liquid, whether it be glycerol'or triethanolamine. However, in theinitial exhaustive oxyalkylation of any product it is usuallydesirableto use a minimum amount of the product so thatconsiderableoxide can be added. This presents the difficulty of gettingeffective stirring at the early stages. For this reasonit isconvenientto add an inert solvent, such as xylene or a high boiling aromaticpetroleum solvent, without differentiating whether one obtains asolution or a slurry, or in the case of'a liquid a suspension ortemporary emulsion. In due course oxyalkylation of the kind hereindescribed produce products which are soluble in either xylene or highboiling aromatic petroleum solvents.

In order to illustrate why the herein contemplated compounds or saidproducts are. cogeneric mixtures and not single chemical compounds, andwhy they must be described in terms of manufacture, and molal ratio orpercentage ratio of reactants, reference is made to a mono hydricalcohol. As has been pointed out previously, and as will be notedhereinafter, on the average the residual polyaminesmay contain as manyas 8 or 9 reactive hydrogen atoms and thus in the early stages ofoxyalkylation. may'result in compounds having 8 or 9 hydroxyl groups.However, for the moment one can forget Whether the reactive hydrogenatoms are attached to nitrogen, or eventually at an intermediate stageare attached to oxygen, and for that matter ignore the plurality ofreactive hydrogen atomsandsimply consider what happens when. amonohydricalcohol is subjected to oxyalkylation.

- If oneselects any hydroxylatedcompound and subjects such compound tooxyalkylation, such as oxyethylation or oxypropylation, itbecomesobviousthat one is really producing a polymer of the. alkylene oxide except forthe terminal group. This is particularly true where the amount of oxideadded is comparatively large, for instance, 10, 20, 30, 40, or 50 units.If such a compound is subjected to oxyethylation so as to introduce 30units of ethylene oxide, it is well known that one does not obtain asingle constituent which, for sakeof convenience, may be indicated asRO(C2H40)30H. cogeneric mixture of closely related homologous compoundsin which the' formula may beshown asthefollowing: RO(.C2H4O)1LH, whereinrz, as far as the statistical a've'ragegoes, i330, but theindividualmembers present in significant amount may vary from instances wheren hasa value of 25. and perhaps less, to a point where n may: represent 351m.more. Such. mixture is, as

a; cogeneric. closely related". series of touching? Instead, one obtainsa butylene oxide,

homologous compounds. Considerable investigation has been made in regardto the distribution curves for linear polymers. Attention is directed tothe article entitled Fundamental Principles of CondensationPolymerization, by Paul J. Flory, which appeared in Chemical Reviews,volume 39, No. 1,, page. 137.

Unfortunately, as has been pointed out by Flory and.

a compound such as the residual higher polyethylene amines.

Although acid catalysts are used in oxyalkylations they are used to alesser extent in the oxyalkylations of basic amines and the like- Undersuch circumstances one may have.to use enough of. the acidic catalyst toneutralize the basicity of the product and convert into a salt. This isnot true where certain clays or prepared earths are used which act asacidic catalyst. In any event, it is my preference to use basiccatalysts such as caustic soda, sodium methylate, or the like.

PART 2' The oxyalkylation of an amine, particularly a primary amine, orsecondary amine or a hydroxylated amine regardless of whether it isprimary, secondary, or tertiary, is comparatively simple and has beendescribed repeatedly in the literature.

If the product is a liquid, such as triethanolarnine, one can proceed totreat with an alkylene oxide such as ethylene oxide, propylene oxide, orbutylene oxide, at least in the early stages if desired without addingany catalyst. Generally speaking, if oxyalkylation is rather extensiveas in the present instance, one requires a cata lyst after the initialstage and it is just as simple to add it from the verybeginning.

The oxypropylation of a polyamine, such as a residual higherpolyethylene amine, is comparatively simple because such products orsimilar products are usually liquids at ordinary temperature andinvariably at oxyalkylation temperaturesn Indeed, the procedure issimply to oxyalkylate without addition of any catalyst if desired andthen when oxyalkylation slows up add the usual basic catalyst, such aspowdered caustic soda or powdered sodium methylate; If] desired, suchcatalyst'can be added at the very beginning. It is also desirable insuch cases where exhaustive oxyalkylation is-concerned to add a diluent,such as xylene, high boiling petroleum solvent, or the like, at the verybeginning. Such solvents usually aremiscible but if not miscible oneobtains a suspension or temporary emulsion and as soon as oxyalkylationhas proceeded to even a slight degree the entire mass is homogeneous.

Specific reference is made to the instant application which is concernedwith ethylene oxide and propylene oxide or the. equivalents. Actually,whether one uses ethylene oxide or propylene oxide or, for that matter,vone preferably starts with a polyamine suspended in the form ofa slurry,an emulsion, a suspension or as a, solution- There would be a slurry inevent the amine: is a solid and insoluble. Inthe present case, however,the amine is a liquid as pointed out.

If desired, one'canemplo'y an alkylene carbonate, such" astethylenecarbonate, butylene. carbonate, or propylene carbonate, for the initialoxyalkylation'. Where such.

initial oxyalkylation has gone far enough to convert the polyamine intoa solvent-soluble product, i. e., soluble in xylene or an aromaticpetroleum solvent, one can then use the oxides. The carbonates, ofcourse, cost more than the oxides and there is no real advantage in mostcases unless one starts with 'an insoluble amine such astris(hydroxymethyl) aminomethane and this does not apply in the presentcase.

In any event, as is well known the oxyethylation of polyamines proceedsas readily as the oxypropylation, and this applies also tooxybutylation, particularly it the straight chain butylene oxide isomersare employed. See, for example, U. S. Patents Nos. 2,679,511, 2,679,512,2,679,513, 2,679,514, and 2,679,515, all dated May 25, 1954, to DeGroote.

It is not believed any examples are necessary to illustrate such wellknown procedure but for purpose of illustration the following areincluded:

Example 1 aa The reaction vessel employed was a stainless steelautoclave with the usual devices for heating, heat control, stirrer,inlet, outlet, etc., which is conventional in this type of apparatus.The capacity was approximately 4 liters. The stirrer was operated at aspeed of approximately 250 R. P. M. There were charged into theautoclave 500 grams of a residual higher polyethylene amine, 300 gramsof xylene, and grams of sodium methylate. The autoclave was sealed,swept with nitrogen gas and stirring started immediately and heatapplied. The temperature was allowed to rise to approximately 150 C. Atthis particular time the addition of propylene oxide was started.Propylene oxide was added continuously at such speed that it wasabsorbed by the reaction as added. The amount added in this operationwas 1500 grams. The time required to add the propylene oxide was twohours. During this period the temperature was maintained at 138 to 150C., using cooling water through the inner coils when necessary andotherwise applying heat if required. The maximum pressure during thereaction was 52 pounds per square inch. Ignoring the xylene and sodiummethylate and considering only theresidual higher polyethylene amine forconvenience, the resultant product represents 3 parts by weight ofpropylene oxide to one part by weight of the residual higherpolyethylene amine. The xylene present represented approximately .6 partby weight.

Example Zaa The reaction mass of Example laa was transferred to a largerautoclave (capacity 15 liters). Without adding any more solvent or anymore xylene the procedure was repeated so as to add another 1500 gramsof propylene oxide under substantially the same operating con ditionsbut requiring about 3% hours for the addition. At the end of this stepthe ratio represented approximately 6 to 1 (ratio propylene oxide toresidual higher polyethylene amine).

ene oxide to the product of Example laa, 1625 grams were added. Thereaction slowed up and required approximately 5% hours, using the sameoperating temperatures and pressures. The ratio at the end of 'the thirdstep was 9.25 parts by weight of propylene oxide per weight of residualhigher polyethylene amine.

methylate added, the autoclave flushed out. as before,

1625 grams of propylene oxide, and the oxyalkylation' was completewithin 3 /2 hours using the same tempera-' ture range and pressure aspreviously. At the end of the reaction the product representedapproximately 12.5 parts of propylene oxide by weight to one part ofresidual higher polyethylene amine.

Having obtained oxypropylated residual higher polyethylene amine theproducts were subjected to oxyethylation in a manner comparable to theoxyethylation of triethanolamines, or for that matter, in the same waythat oxypropylated sucrose is subjected to oxyethylation in the mannerdescribed in U. S. Patent No. 2,652,394, dated September 15, 1953, to DeGroote. Indeed, the procedure is comparatively simple for the reasonthat one is working with a liquid and also that ethylene oxide is morereactive than propylene oxide. As a result, usingthe same amount ofcatalyst one can oxyethylate more rapidly and usually at a lowerpressure.

The same procedure using a mixture of residual higher polyethyleneamines in xylene was employed in connection with ethyleneoxide and thesame mixture on a percentage basis was obtained as in the above exampleswhere propylene oxide and residual higher polyethylene amine were used.

In the preceding procedures one oxide has been added and then the other.One need not follow this procedure. The two oxides can be mixed togetherin suitable proportions :and subsequently subjected to jointoxyalkylation so as to obtain products coming within the specifiedlimits. In such instances, of course, the oxyalkylation may be describedas random oxyalkylat'ion insofar that one cannot determine the exactlocation of the propyleneoxide or ethylene oxide groups. In suchinstances the procedure again is identically the same as previouslydescribed and, as a matter of fact, I have used such methods inconnection with residual higher polyethylene amine.

Actually, residual higher polyethylene amine at times amines andpropylene oxide on the other hand, and re-- act with the other oxide.Note line CC-DD which indicates that in the binary reaction productobtained from residual higher polyethylene amines and ethylene oxide oneemploys approximately 66.6% to 96.5% of ethylene oxide and approximately3.5% to 33.4% of residual higher polyethylene amines.

Similarly, if one refers to the line AA-BB it means one would employfrom 1.95% of residual higher polyethylene amine up to 14.3% of residualhigher polyethylene amine and from 85.7% of propylene oxide up.

to 98.05% of propylene oxide.

In other operations I have proceeded to do as follows:' Mixed the liquidresidual higher polyethylene amine with an aromatic petroleum solventand with powdered caus-S I have stirred this mixture at to C.

tic soda. for a short period of time, approximately one-half hour,

'fiushed out with nitrogen, and then subjected to vacuum so as toeliminate any moisture. I then started to oxypropylate and continueduntil oxypropylation was complete and then immediately followed withethylene oxide. In these examples the amount of materials used areindicated in pounds-and in each instance of course, asuitable'sizeautoclavewas used. Although the oxyalkylation' startedunder vacuum the maximum pressure at any time wasabout 10 to 15 pounds.vAn efiicient agitating-"dea vice was used and stirring. speed wasapproximately '35ll RJPi Ml These data.- covering nine oxyalkylationsare included in Table I, immediatelyfollowing. The time periods are:shown. Incidentally, I have repeated these same operations usingethylene oxide first and then propylene'oxide and I have also mixedthe-two oxides and completed the same nine oxyalky lationsundersubstantially the same conditions.

is 'deseribed 'alsciin detail ahove. AIl one need d is employ suchconventional. oxyalkylation:procedure=.to obtain productscorrespondingrm'the compositions asde fined. Attention. is again.directed tothe fact that: one need. not add the entire amount of eitheroxide at one time but that. an smallv .pontion. ofione could added andthen another smalL portiont ofl the other; and the process repeated. 1

i For. purpose of illustration I have prepared examples TABLE 1Hl'ghgifg g boiling Caustic Propylene Ethylene Time, Temp., Maximum Ex.No. g g argoniatic soda, lbs. oxide, lbs. oizde, hrs. 0. press, 111:. paro eum 5. per sq. amine solvent, lbs.

Referring again to the ratio of the initial reactants based on thetrapezoid in attached drawing, I have calculated. the percentage of thethree. initial reactants for 35.

the. points A, B, C, D, E,.and F, and Nos- 1 through 14, inclusive. Ihave also calculated initial binary mixtures corresponding in essence tothe lines CC-DD and AABB, all of which appears in 'self-explanatory formin Table- II, immediately following.

in three difierent ways corresponding to the-compositions on thedrawing. In the first series propylene oxide and ethylene oxide weremixed; this series is indicatedas Aa, Ba, etc., through and including147:; in the second series 'proplyene oxide was used'first followed byethylene oxide and this series is indicated as Ab,.B?.-, etc., through40 and including 14b; and finally in :a third series, ethylene TABLE IITertiary mixture, percent basis Binary: intermediate mixtures, percentbasis Points 011 Residual Residual Residual boundary higher PropylEthylhigher Propylhigher Dob Ethylyethylene me we yethylene 1 yethyleneamine oxide oxide am e OXldB' amine oxide 1. 75' 88. 25 10.0. 1. 95 98.05' 14. 90 85. 1 1. 75 50. 0 48. 25 8. 38 96. 62 3.5 96. 5" 5. 0 75. 020. 0 6 24 93. 76 29. 0 80. 0 5. 0 55. 0 40. U 8. 321 91. 68 11. 1 88. 910. 0 70. 0 20. 0 12. 5 87. 5 33. 4 66. 6 10. 0 60. 0 30. O 14. 3 85. 725. O 75'. 0 4. 72 76. 4 18. 88v 5. 8 94. 2 20. 0 80. 0 3. 62 78. 3 18.15 4'. 42 95. 58 13. 1 86. 9 3. 07 66. 3 30. 63 4'. 43 95. 57 9. 1 90.97 2. 84 83. 0 14; 16 3. '51 96. 49 l6. 7 83. 3 2. 66 57. 5 39. 84 4.42. 95. 58 6. 25 93. 75 2. 48 72. 6 24. 92 3. 3 96. 7 9.04 90. 96 2. 2164. 7 33. 09' 3. 3 96.7 6. 26 93. 74 2. 16 81. 5 16. 54 2. 58 97. 42 11.88. 45 1. 97 74. 5 23. 53 2. '58 97. 42 V 7. 73 92. 2 4; 0 61. 0 35. 06. 17 93. 83' 10. 28 89. 72 1. 8 83. i) 16. 0 2. 12 9 7. 88 10. 1 89. 97. 0 70. 0 23. 0 9; 1 89. 9 23. 35 76. 8.0. 57. 0. 35. 0 12.3 87; 7 18.6 81. 4 9. 0 65. 0 26. 0 12. 15 87. S5 25. 7 74. 3

As previously pointed out, the oxyalkylationof. residual higher.polyethylene amine or similar hydroxylated monoor poly amines has beendescribed in the literature and oxide was used first followed bypropylene oxide and this series is indicated as Ac, Bc, etc., through.and. including 140. This relationship is shown Table III.

TABLE III Composition Composition Composition where oxides wherepropylwhere ethyl- Composltlon corresponding are mixed ene oxide eneoxide to following point prior to oxyused first folused firstrolalkylation lowed by ethlowed by proylene oxide pylene oxide Aa Ab AcBa El) E Ca Cb Cc Da Db Dc Ea Eb Ec Fa Fb Fa 1a 1b 10 2a 2b 2a 3a 3b 304a 4b 4c 5a 5b 5e 6a 6b 60 7a 7b 70 8a 8b 8c 9a 9b 90 10a 10b 10:: 11a11b 11c 12a llb 12c 13a 13b 13c 14a 14b 14c The products obtained by theabove procedure usually show some color varying from a light amber to apale straw. They can be bleached in the usual fashion using bleachingclays, charcoal, or an organic bleach, such as peroxide or peraceticacid, or the like.

There are certain variants which can be employed without detracting fromthe metes and bounds of the invention, but for all practical purposesthere is nothing to be gained by such variants and the result is merelyincreased cost. For instance, any one of the two oxides can be replacedto a minor percentage and usually to a very small degree, by oxide whichwould introduce substantially the same group along with a side chain,for instance, one could employ glycidyl methyl ether, glycidyl ethylether, glycidyl isopropyl ether, glycidyl butyl ether or the like.

Increased branching also may be effected by the use of an imine insteadof a glycide, or a methyl glycide. Thus one can use ethylene imine, orpropylene imine in the same way described for glycide or methyl glycide.An additional efiect is obtained due to the basicity of the nitrogenatom. The same thing is true as far as the inclusion of nitrogen atomsif one uses a compound of the kind previously described such as adialkylaminoepoxypropane. Excellent products are obtained by reactingresidual higher polyethylene amines, with one to 10 moles of ethyleneimine and then proceeding in the same manner herein described.

In the hereto appended claims reference has been made to glycol ethersof residual higher polyethylene amines. Actually it well may be that theproducts should be referred to as polyol ethers of residual higherpolyethylene amines in order to emphasize the fact that the finalproducts of reaction have more than two hydroxyl radicals. However, theproducts may be considered as hypothetically derived by reaction ofresidual higher polyethylene amines with the glycols, such as ethyleneglycol, butylene glycol, propylene glycol, or polyglycols. For thisreason there seems to be a preference to use the terminology glycolethers of residual higher polyethylene amines.

In a trapezoid such as A, B, D, C, the area can be divided convenientlyinto five portions by first drawing two lines from the shorter of thetwo parallel sides perpendicular so as to intersect the other longerparallel line in two places, thus dividing the trapezoid into twotriangles and a rectangle. The rectangle then obviously can be dividedinto three portions of the same size by drawing two additional lines,all of which is shown in the drawing on a larger scale and in dottedlines only. In the hereto attached claims the area within the upper apexof the trapezoid refers to the area within such upper triangle; the areawithin the lower apex of the trapezoid refers to such lower triangle.The area in the center of the trapezoid refers to the area defined bythe middle rectangle. The area. of one rectangle is defined by beingbetween the upper apex and the center rectangle, and the other by beingbetween the lower apex and the center rectangle, all of which isperfectly plain by refer-. ence to the drawing' An attempt to drawadditional lines andto number them in the same trapezoid A, B, D, C,would only tend towards confusion and thus the present means is beingemployed to point out the various areas which in turn, appearin thesub-generic claims hereto appended. Thus in the drawing, the areadesignated V corresponds to the area within the upper triangle, the.area W corresponds to the area within the lower triangle, the areaX'corresponds to that of the middle rectangle, and the areas Y and Zcorrespond to those of the other rectangles.

PART 3 As to the use of conventional demulsifying agents, reference ismade to U. S. Patent No. 2,626,929, dated Ianuary 27, 1953, to DeGroote, and particularly to Part 3. Everything that appears thereinapplies with equal force and efie ct to the instant process, noting onlythat where reference is made to Example 13b in said text beginning incolumn 15 and ending in column 18, reference should be to Example 5bherein described.

Having thus described my invention, what I claim as new and desiretoobtain by Letters Patent, is:

l. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a cogeneric mixture of a homologous series of glycol ethers ofresidual nondistilled polyethylene polyamines having at least 6 nitrogenatoms obtained in the production of polyethylene polyamines from ammoniaand ethylene dichloride; said cogeneric mixture being derivedexclusively from said residual polyethylene polyamines, propylene oxideand ethylene oxide in such weight proportions so the average compositionof said cogeneric mixture, stated in terms of initial reactants, liesapproximately within the trapezoid of the accompanying drawing in whichthe minimum residual polyethylene polyamine content is at least 1.75%and which trapezoid is identified by the fact that its area lies withinthe straight lines A, B, F, E.

2. The process of claim 1 with the proviso that oxyalkylation takesplace in presence of an alkaline catalyst. 3. The process of claim 1with the proviso that oxyalkylation takes place in presence of analkaline catalyst grid that at least part of the propylene oxide isadded 4. The process of claim 1 with the proviso that oxyalkylationtakes place in presence of an alkaline catalyst and that all thepropylene oxide is added first.

5. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to a demulsifying agentincluding a cogeneric mixture of a homologous series of glycol ethers ofresidual uondistilled polyethylene polyamines having at least 6 nitrogenatoms obtained in the production of polyethylene polyamines from ammoniaand ethylene dichloride; said cogeneric mixture being derivedexclusively from said residual polyethylene polyamines, propylene oxideand ethylene oxide in such weight proportions so the average compositionof said cogeneric mixture. stated in terms of initial reactants, liesapproximately within the trapezoid of the accompanying drawing in whichthe minimum residual polyethylene polyamine content is at least 1.75%and which trapezoid is identified by the fact that its area lies withinthe straight lines A, B, D, C; with the proviso that all the propyleneoxide is added first in presence of an alkaline catalyst.

6. The process of claim 5 with the proviso that the reactant compositionapproximates a point in the area cor ll responding with V within theupper apex of the trapezoid A,B,D,.C. I v

7. The process of claim with the .provisothat the reactant compositionapproximates a point in the area corresponding with W within the lowerapex of the trapezoid A, B, D, C.

8. The process of claim 5 with theproviso that the reactant compositionapproximates :a point in'the area corresponding withX of the centralpart of the trapezoid A,B,D,C. 1 p

9. The process of claim 5 with the proviso that the reactant compositionapproximates a point in the area corresponding with Y between thecentral part of the trapezoid A, B, C, D, and the upper apex.

10. The process of claim 5 with the proviso that the reactantcomposition approximates a point in the area corresponding with Zbetween the central part of the trapezoid A, B, D, C, and the lowerapex.

11. A process for breaking petroleum emulsions of the I mixture of ahomologous series of glycol ethers of residual residual polyethylenepolyamine content is at least 1.75%

and which trapezoid is identified by the fact that its area lies withinthe straight lines A, B, F, E; with the proviso that the hydrophileproperties'of said cogeneric mixture in an equal Weight of xylene aresufiicient to produce an emulsion when said xylene solution is shakenvigorously with one to three volumes of water.

12. The process of claim 11 with the proviso .thatoxyalkylation takesplace in presence of an alkaline catalyst.

13. The process of claim 11 with the proviso'that oxyalkylation takesplace in presence of an alkaline catalyst and that at least part of thepropylene oxide is added first.

14. The process of claim 11 with the proviso that oxyalkylation takesplace in presence of an alkaline catalyst and that all the propyleneoxide is added first.

15. A process for breaking petroleum emulsions of the waterein-oil typecharacterized by subjecting the emulsion to a .demulsifiyingagentincluding a cogeneric nitrogen atoms obtained in the production ofpolyethylene polyamines from ammonia and ethylene dichloride; said cogeneric mixture'being derived exclusively from said residual polyethylenepolyamines, propylene oxide and ethylene oxide in such weightproportions so the average composition of said cogeneric mixture, statedin terms of initial reactants, lies approximately within the trapezoidof the accompanying drawing in which the minimum residualpolyethylenepolyamine content is at least 1.75

and which trapezoid is identified by the fact that its area lies Withinthe straight lines, A, B, D, C; with the proviso that all the propyleneoxide is added first in the presence of an alkaline catalyst; and withthe further proviso that the hydrophile properties of said cogenericmixture in anrequal weight of xylene are sufiicient to produce anemulsion when said xylene solution isf shaken vigorously with one tothree volumes of wate V 16. The process of claim 15 with the provisothat the reactant'composition approximates a point in the areacorresponding with V Within the upper apex of the trapezoid A, B, D, C.

17. The process of claim'lS with the proviso that the reactantcomposition approximates a pointin the area corresponding with W withinthe lower apex of the trapezoid A, B, D, C.

18. The process of claim 15 with the proviso that the reactantcomposition approximates a point in the area gprresponding with X of thecentral part of the trapezoid A: BL C i '19. The process of claim 15with the proviso that the reactant .compositionrapproximates a point inthe area corresponding with Y between the central part of the trapezoidA, B, D, C, and the upper apex. 20. The process of claim 15 with theproviso that the reactant composition approximates a point in the areacorresponding with'Z between the central part of the trapezoid A, B, D,C, and the lower apex.

References Cited in the file of this patent. UNITED STATES PATENTS2,457,634 Bond et al. Dec. 28, 1948 2,552,530 De Groote May 15, 1951"2,552,531 De Groote May 15, 1951 2,589,200 Monson Mar. 11, 19522,622,099 Ferrero et a1. Dec, 16, 1952 2,649,483 Huscher et a1 Aug. 18,1953 A... ar

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENTINCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OFRESIDUAL NONDISTILLED POLYETHYLENE POLYAMINES HAVING AT LEAST 6 NITROTENATOMS OBTAINED IN THE PRODUCTION OF POLYETHYLENE POLYAMINES FROM AMMONIAAND ETHYLENE DICHLORIDE; SAID COGENERIC MIXTURE BEING DERIVEDEXCLUSIVELY FROM SAID RESIDUAL POLYETHYLENE POLYAMINES, PROPYLENE OXIDEAND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITIONOF SAID COGENERIC MIXTURE, STATE IN TERMS OF INITIAL REACTANTS LIESAPPROXIMATELY WITHIN THE TRAPEZOID OF THE ACCOMPANYING DRAWING IN WHICHTHE MINIMUM RESIDUAL POLYETHYLENE POLYAMINE CONTENT IS AT LEAST 1.75%AND WITH TRAPEZOID IS IDENTIFIED BY THE FACT THAT ITS AREA LIES WITHINTHE STRAIGHT LINES A,B,F,E.